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United States Patent | 5,166,012 |
Rossouw ,   et al. | November 24, 1992 |
The invention provides a hydrogen manganese oxide compound. It has manganese cations and oxygen anions arranged in a framework having a hollandite-type structure and defining channels. Cations in the channels are confined to manganse, hydrogen and/or lithium cations. The ionic ratios of lithium:manganese cations and of hydrogen:manganese cations are respectively at most 0.05:1 and at least 0.01:1.00. The invention also provides a method of making said compound; a lithium manganese oxide compound derived from said hydrogen manganese oxide compound and a method of synthesising it therefrom; and electrochemical cells employing said hydrogen manganese oxide and lithium manganese oxide compounds as active cathode materials.
Inventors: | Rossouw; Margaretha H. (Pretoria, ZA); Thackeray; Michael M. (Pretoria, ZA) |
Assignee: | Technology Finance Corporation (Proprietary) Limited (Sandton, ZA) |
Appl. No.: | 694787 |
Filed: | May 2, 1991 |
May 17, 1990[ZA] | 90/3797 | |
Feb 19, 1991[ZA] | 91/1225 |
Current U.S. Class: | 429/224; 423/599 |
Intern'l Class: | H01M 004/50; C01G 045/12 |
Field of Search: | 429/224 423/599,605 |
2885262 | May., 1959 | Fleischer et al. | 423/605. |
3320157 | May., 1967 | Arey et al. | 423/605. |
4758484 | Jul., 1988 | Furukawa et al. | 429/224. |
4959282 | Sep., 1990 | Dahn et al. | 423/605. |
4975346 | Dec., 1990 | Lecerf et al. | |
Foreign Patent Documents | |||
279235 | Aug., 1988 | EP. | |
2656957 | Jul., 1991 | FR. | |
2221213A | Jan., 1990 | GB. | |
2234233 | Jan., 1991 | GB. |
Volnov Electrochimica Acta vol. 27, No. 7, "MnO.sub.2 Structure and Activity", pp. 833-835, Jul. 1982. Nohma, Journal of Power Sources vol. 26, No. 3/4 "Manganse Oxides for a Lithium Secondary Battery-Composite Dimensional Manganese Oxide (CDMO)", pp. 389-396, May 1989. Ohzuku, T., et al., J. Electrochem. Soc., 138: 360-265 (Feb., 1991). Parant, J.-P., et al., J. Solid State Chem., 3:1-11 (1971). Parida, K. M. et al., Electrochimica Acta, 26:435-443 (1981). Wells, A. F., Structural Inorganic Chemistry, 4th ed., Clarendon Press, Oxford, 1975, pp. 459-460. |
TABLE ______________________________________ Invention Reference Intensity Intensity h k l d (.ANG.) (cps) h k l d (.ANG.) (cps) ______________________________________ 110 6.913 99 110 6.940 26 200 4.889 92 200 4.908 32 220 3.457 3 220 3.470 11 310 3.092 100 310 3.104 68 101 2.739 5 101 2.734 1 400 2.444 40 400 2.454 7 211 2.389 61 211 2.389 100 330 2.304 20 330 2.313 3 420 2.186 13 420 2.195 7 301 2.147 24 301 2.148 18 321 1.9655 6 510 1.9174 19 510 1.9249 4 411 1.8236 51 411 1.8262 12 440 1.7284 6 440 1.7351 1 530 1.6767 <1 530 1.6833 2 600 1.6295 36 600 1.6358 12 431, 501 1.6129 36 431 1.6161 5 620 1.5459 4 620 1.5519 1 521 1.5317 60 521 1.5350 9 002 1.4265 12 002 1.4235 5 611 1.4004 3 611 1.4038 1 112 1.3971 3 550, 710 1.3827 8 550 1.3881 1 202 1.3694 6 202 1.3671 1 ______________________________________